JPH0859549A - Etherified polyhydric alcohol fatty acid ester and its production - Google Patents

Abstract

PURPOSE: To obtain a new etherified polyhydric alcohol fatty acid ester useful as a base for cosmetics, an emulsifier, a lubricating agent, a lubricant, an intermediate, etc., for producing etherified polyhydric alcohols. CONSTITUTION: A compound of formula I [G is a residue obtained by removing H of all hydroxyl groups in polyhydric alcohol having >=3 hydroxyl groups; A is formula II or III (R is R' or CH2 OR'; R' is a 1-36C alkyl or an alkenyl); B is H or a 1-11C acyl; the sum of x and y is number of hydroxyl of polyhydric alcohol in G and x and y are each >=1], e.g. pentaerythritolmonoisostearyl glyceryl ether monoacetate. Furthermore, the compound of formula I is obtained by reacting a polyhydric alcohol fatty acid ester of the formula G(B)z [z is number of hydroxyl of polyhydric alcohol] with an epoxy compound of formula IV.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a glyceryl etherified polyhydric alcohol or a hydroxyalkyl etherified polyhydric alcohol which is itself useful as a base for cosmetics, an emulsifier, a lubricant, an oil, etc., and used for the same purpose. The present invention relates to an etherified polyhydric alcohol fatty acid ester that is also useful as an intermediate for producing a polyhydric alcohol, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
BACKGROUND ART Polyol ethers such as polyoxyalkylene alkyl ethers and polyoxyalkylene ethers of sorbitan esters, and alkyl etherified polyhydric alcohols are used as bases, emulsifiers, lubricants, oils and the like for cosmetics and cosmetics.

However, among these, polyol ethers are produced by the addition reaction of alkylene oxides such as ethylene oxide and propylene oxide, and the obtained product is a mixture of those having various polyoxyalkylene chain lengths, It is difficult to synthesize a high-purity product, and sufficient performance may not be obtained when it is used for cosmetics, perfumes and the like. Further, among the alkyl etherified polyhydric alcohols, there are some compounds having good properties (see glyceryl etherified polyhydric alcohols and hydroxyalkyl etherified polyhydric alcohols, JP-A-5-9).
No. 84), most of them are solids having a high melting point, the hydrophilic group and the lipophilic group are improperly balanced, it is difficult to uniformly disperse them in water, and the compatibility with various solvents is poor. There were cases.

Therefore, there has been a demand for the development of a compound having superior performance as a base for cosmetics, an emulsifier, a lubricant, an oil, etc., which can be easily manufactured at a low cost.

The glyceryl etherified polyhydric alcohol or the hydroxyalkyl etherified polyhydric alcohol is conventionally produced by reacting an epoxy compound such as glycidyl ether with a polyhydric alcohol in the presence of a catalyst. Therefore, the etherified polyhydric alcohol is obtained as a mixture of various etherified polyhydric alcohols having different etherification degrees, such as a 1 mol adduct obtained by reacting an epoxy compound with 1 mol and a 2 mol adduct obtained by reacting with an epoxy compound. However, since the characteristics of the compound differ depending on the difference in the degree of etherification (number of moles added), it is desirable to use etherified polyhydric alcohols having a uniform degree of etherification depending on the application. For example, the cosmetic component is preferably a 1-mol adduct, and in order to obtain a product with a high 1-mol adduct content, it is necessary to increase the excess ratio of the polyhydric alcohol with respect to the epoxy compound. There was a problem that I had no choice.

[0006]

Under these circumstances, the inventors of the present invention have conducted diligent research, and as a result, have shown the following etherified polyhydric alcohol fatty acid ester (1) obtained by reacting a polyhydric alcohol fatty acid ester with an epoxy compound. Is useful as an intermediate for the production of etherified polyhydric alcohol conventionally used as a cosmetic ingredient, and efficiently produces an etherified polyhydric alcohol having a desired degree of etherification through the compound (1). The present invention has been completed, and it was found that the compound itself has excellent properties as a base material for cosmetics, an emulsifier, a lubricant, an oil agent and the like.

That is, the present invention relates to an etherified polyhydric alcohol fatty acid ester represented by the following general formula (1). G (A) _x (B) _y (1) [In the formula, G represents a residue excluding hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having three or more hydroxyl groups, and x A's are the same. Or it may be different

[0008]

[Chemical 7]

(R is R'or --CH ₂ OR '(R' is 1 carbon atom
~ 36 linear or branched alkyl or alkenyl groups). ), The y B's may be the same or different and each represents a hydrogen atom or an acyl group having 1 to 11 carbon atoms, at least one of which is an acyl group. x and y
Are numbers of 1 or more, the sum of which is the number of hydroxyl groups of the polyhydric alcohol in G. ]

The etherified polyhydric alcohol fatty acid ester (1) of the present invention comprises a polyhydric alcohol fatty acid ester (2) and an epoxy compound (3), for example, according to the following reaction formula.
It is produced by reacting with.

[0011]

Embedded image

(Wherein G, A, B, x, y, and R have the same meanings as described above, z represents the number of hydroxyl groups of the polyhydric alcohol in G, and at least one is contained in z Bs). Each hydrogen atom and an acyl group are included.)

The polyhydric alcohol fatty acid ester (2) used in this reaction is synthesized by a conventionally known method. For example, a polyhydric alcohol having 3 or more hydroxyl groups,
Fatty acids, fatty acid esters, fatty acid chlorides, fatty acid anhydrides and the like, in the absence of solvent or in a solvent such as toluene, xylene, without a catalyst or p-toluenesulfonic acid, sulfuric acid, sodium hydroxide, potassium hydroxide, sodium acetate, The polyhydric alcohol fatty acid ester (2) is obtained by reacting at 100 to 200 ° C. in the presence of a catalyst such as sodium phosphate, preferably sodium acetate. The polyhydric alcohol fatty acid ester (2) can also be obtained by transesterifying the polyhydric alcohol fatty acid ester with the polyhydric alcohol.

Examples of the polyhydric alcohol having 3 or more hydroxyl groups used in this reaction include pentaerythritol, sorbitol, mannitol, maltitol, glycosides, glycerin and the following general formulas.

[0015]

[Chemical 9]

(In the formula, a represents a number of 2 to 20), polyglycerol, erythritol, inositol, xylitol, dipentaerythritol, tripentaerythritol, heptitol, octitol, 1,
2,3,4-pentanetetrol, 1,3,4,5-hexanetetrol, sorbitan, mannitane, raffinose, gentianose, xylose, galactose, mannose, maltose, sorbiose, maltotriose, maltotetraose, maltopenta Aus, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, sucrose, fructofuranose, fructopyranose, glucopyranose, alkylene oxide adducts thereof and the like can be mentioned.

Of these, examples of glycosides include (a) glucose, galactose, fructose,
Monosaccharides such as mannose and xylose, disaccharides such as maltose, isomaltose, lactose and sucrose, or polysaccharides such as cellulose, starch and amylose, and (b) methanol, ethanol, propanol, octanol, decyl alcohol and dodecyl alcohol. , Oleyl alcohol, alcohols such as 2-ethylhexanol, or polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, and sorbitol are obtained by a known means for reacting them in the presence of an acid catalyst. Can be mentioned. Specifically, methyl glucoside, ethyl glucoside, propyl glucoside, octyl glucoside, decyl glucoside, dodecyl glucoside, oleyl glucoside, 2-ethylhexyl glucoside, methyl maltoside, alkyl maloside such as ethyl maltoside; 2-hydroxypropyl glucoside, 2,3-dihydroxypropyl glucoside, 2-
Examples thereof include hydroxyalkyl glycosides such as hydroxyethyl glucoside; alkyl ether glycosides such as methoxyethyl glucoside and ethoxyethyl glucoside; oligosaccharides having a reduced reducing terminal such as maltitol and lactitol.

Further, polyglycerin is diglycerin,
A polyglycerin obtained by condensing glycerin by a known method, as typified by triglycerin, tetraglycerin, pentaglycerin and the like. The polyglycerin used in the present invention is a polyglycerin having an average degree of condensation a of glycerin of 2 to 20, but when polyglycerin having a high degree of condensation is used, hydrophilicity becomes too high and sufficient performance is obtained. In some cases, it is desirable to use polyglycerin in which a is 2 to 10, and more preferably a is 2 to 4.

When the alkylene oxide adducts of these polyhydric alcohols are used as the polyhydric alcohol having 3 or more hydroxyl groups, the alkylene oxide preferably has 2 to 4 carbon atoms, and the average addition per hydroxyl group thereof. The number of moles is preferably 1 to 10 moles.

Of these polyhydric alcohols, preferred are pentaerythritol, sorbitol, mannitol, glycosides, glycerin, polyglycerin and alkylene oxide adducts thereof, and more preferred are pentaerythritol, glycerin and a.
= 2 to 4 polyglycerin, and particularly preferred is pentaerythritol. 3 hydroxyl groups
The polyhydric alcohols having two or more can be used alone or in combination of two or more.

Further, the polyhydric alcohol used in the present invention may contain impurities other than the polyhydric alcohol corresponding to the intended product, but if there is no practical problem, use the polyhydric alcohol as it is. If it is necessary to improve the performance and quality of the product, it can be purified by a conventionally known purification method before use.

For example, pentaerythritol may contain dipentaerythritol or tripentaerythritol condensed with pentaerythritol, and sorbitol or mannitol may contain a small amount of reducing sugar such as glucose. When used as it is, a small amount of these fatty acid esters of impurities are by-produced, but it can be used after purification by a crystallization operation or the like, if necessary.

As the fatty acid, fatty acid ester, fatty acid chloride, fatty acid anhydride and the like to be reacted with these polyhydric alcohols, any fatty acid moiety having a carbon number of 1 to 11 can be used, but after hydrolysis From the viewpoint of ease of post-treatment, those having 2 to 4 carbon atoms, particularly acetic acid, are preferable. Further, as the polyhydric alcohol fatty acid ester to be reacted with the polyhydric alcohol in the case of transesterification,
A product obtained by reacting a polyhydric alcohol with a fatty acid or the like as described above can be used.

The polyhydric alcohol fatty acid ester (2) obtained as above is prepared from various ester compounds such as polyhydric alcohols, monoesters in which 1 mol of fatty acid is added to polyhydric alcohol, and diesters in which 2 mols of fatty acid are added. Although it is obtained as a mixture, there is usually no problem if such a mixture is used as it is for the reaction. However, particularly when a highly pure product is required, it may be isolated by performing purification by chromatography or the like.

An example of the reaction for producing pentaerythritol monoacetate is as follows. That is, according to the following reaction formula A, 1 to 3 mol times acetic acid with respect to pentaerythritol is reacted without solvent or in a solvent such as toluene or xylene in the presence of a catalyst such as sodium acetate at a reflux temperature, if necessary. Alternatively, according to the following reaction formula B, 0.5 to 0.5 with respect to pentaerythritol.
A mixture containing pentaerythritol monoacetate as a main component is obtained by reacting 2 mole times pentaerythritol tetraacetate in the absence of solvent or in a solvent such as toluene or xylene in the presence of a catalyst such as sodium acetate at a reflux temperature, if necessary. To be

[0026]

[Chemical 10]

Epoxy compound (3) used in the present invention
Is the following general formula (3a) or (3b)

[0028]

[Chemical 11]

(In the formula, R'has the same meaning as described above.)
The glycidyl ether represented by the general formula (3b) is preferable. The alkyl group represented by R ′ preferably has 6 to 36 carbon atoms, and more preferably has a branched chain. Particularly preferred alkyl groups are those represented by the following general formula (a) or (b):

[0030]

[Chemical 12]

(In the formula, the sum of p and q is 13 to 33.
Is an integer of 0 to 33, and r and s are integers of 0 to 31 whose sum is 11 to 31, respectively. And a group represented by the general formula (a) is preferable. Further, the alkenyl group of R'is preferably one having 6 to 36 carbon atoms, and among them, a hexadecenyl group, an octadecenyl group (particularly an oleyl group) and the like are preferable.

Specific examples of preferred R'include hexyl group, octyl group, hexadecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group (isostearyl group), methyloctadecyl group, methylbehenyl group, ethyl group. Hexadecyl group, ethyloctadecyl group, ethylbehenyl group, butyldodecyl group, butylhexadecyl group, butyloctadecyl group, hexyldecyl group, heptylundecyl group, octyldodecyl group, decyldodecyl group, decyltetradecyl group, dodecylhexadecyl group Group, tetradecyl octadecyl group, hexadecenyl group, octadecenyl group (especially oleyl group) and the like.

The reaction molar ratio of the polyhydric alcohol fatty acid ester (2) and the epoxy compound (3) used in the present invention is appropriately selected according to the degree of etherification of the target etherified polyhydric alcohol fatty acid ester (1). be able to. For example, in order to obtain a product having a high content of 1 mol of adduct, it is preferable to add the polyhydric alcohol fatty acid ester (2) in excess at a ratio of 1.0: 1.0 to 5.0: 1.0. Considering the amount of adduct produced and the recovery of the polyhydric alcohol fatty acid ester (2), 1.2: 1.0-
A ratio of 3.0: 1.0 is preferable. Further, in the case of obtaining a high content of 2 mol adduct, 0.4: 1.0-
It is preferable to make the epoxy compound (3) excessive in a ratio of 1.0: 1.0, and considering the production amount of the 2 mol adduct, 0.5: 1.0 to 0.7: 1.0. Is particularly preferable.

This reaction can be carried out without a solvent, but an organic solvent can be used for the purpose of assisting the mixing of the raw materials. Examples of such an organic solvent include hexane, toluene, xylene, chloroform, 2-methyl-2-propanol, cyclohexane, ethyl acetate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and the like, polyhydric alcohol fatty acid ester. It is preferable to use 0.1 to 10.0 times the amount of (2).

As the catalyst, an acid catalyst or a basic catalyst generally known as an epoxy group reaction catalyst can be used. When a basic catalyst is used, the etherified polyhydric alcohol fatty acid produced as a side reaction is produced. It is preferable to use a base catalyst because the decomposition reaction of the ether bond of the ester (1) and the dehydration reaction of the hydroxyl group can be suppressed. The base catalyst is not particularly limited, but from the viewpoint of reactivity and economy, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride, sodium acetate, sodium carbonate and the like are preferable,
Particularly preferred is sodium acetate. These base catalysts are added in an amount of 0.01 to 20.
It is preferably used in an amount of 0% by weight, particularly 0.1 to 10.0% by weight.

The reaction is carried out at 50 to 250 ° C, preferably 80 to 200 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 250 ° C, the product is colored, which is not preferable.

In this reaction, when water is present in the reaction system, the epoxy group of the epoxy compound (3) reacts with water to form glyceryl ether and the like, so that the polyhydric alcohol fatty acid ester (2) is heated. After the polyhydric alcohol fatty acid ester (2) is dissolved or dispersed in an organic solvent, it is heated to blow dry nitrogen gas, or it is dehydrated by heating under reduced pressure to remove water,
It is preferable to add and react the epoxy compound (3).

Further, in this reaction, since there are two reaction points for the epoxy compound (2), the obtained etherified polyhydric alcohol fatty acid ester (3) is a mixture having an A group having the above-mentioned two kinds of structures. Becomes That is,
An example of the reaction in the case of using pentaerythritol monoacetate as a raw material to obtain a 1 mol adduct is as follows.

[0039]

[Chemical 13]

After completion of the reaction, the etherified polyhydric alcohol fatty acid ester (1) of the present invention can be obtained from the reaction solution by a method such as neutralization, filtration, distillation, extraction, etc., which is a monoether body, a diether body or the like. , A mixture of various ethers. The compound (1) of the present invention can be blended in a cosmetic composition as it is without further purification, or can be used as an intermediate for producing an etherified polyhydric alcohol, but if necessary, It is also possible to purify and use the preferred mono- or diether form as a cosmetic ingredient according to a conventional method such as silica gel column chromatography, solvent extraction and the like.

When the compound (1) of the present invention is used as a cosmetic ingredient, the compounding amount of the compound (1) of the present invention is 0.1 to 20% by weight, preferably 0.5 to 10% by weight in the cosmetic. .

In the cosmetic of the present invention, in addition to the above-mentioned compound (1) of the present invention, components used in ordinary cosmetics, for example, ethylene glycol, diethylene glycol, triethylene glycol, and further polyethylene glycols, propylene glycol and diethylene glycol. Propylene glycol,
Further polypropylene glycols, 1,3-butylene glycol, butylene glycols such as 1,4-butylene glycol, glycerin, diglycerin, further polyglycerins, sorbitol, mannitol,
Sugar alcohols such as xylitol and maltitol, ethylene oxide (hereinafter abbreviated as “EO”) adduct of glycerins, propylene oxide (hereinafter abbreviated as “PO”) adduct, EO and PO adducts of sugar alcohols, galactose, Monosaccharides such as glucose and fructose and their EO,
Polysaccharides such as PO adducts, maltose, lactose and their EO, polyhydric alcohols such as PO adducts; hydrocarbons such as liquid paraffin, squalane, vaseline, solid paraffin, olive oil, jojoba oil, evening primrose oil, coconut oil, beef tallow Natural oils such as isopropyl myristate, cetyl isooctanoate, ester oils such as neopentyl glycol dicaprate, silicone oils such as methyl silicone and methylphenyl silicone, oily components such as higher fatty acids such as isostearic acid and oleic acid; Polyoxyethylene (hereinafter abbreviated as "POE") alkyl ether, POE
Branched alkyl ether, POE sorbitan ester, P
OE glycerin fatty acid ester, POE hydrogenated castor oil,
Nonionic surfactants such as sorbitan esters, glycerin fatty acid esters, polyglycerin fatty acid esters, anionic surfactants such as phosphoric acid-based, sulfonic acid-based, sulfuric acid-based, carboxylic acid-based, and other amphoteric surfactants, positive Ionic surfactants; vitamins, bactericides such as triclosan and trichlorocarban, anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate, antidandruff agents such as zinc pyrithione and octopirox, activators, UV absorbers, etc. Drugs: preservatives such as methylparaben and butylparaben, foaming agents such as alkylamine oxides and fatty acid alkanolamides, inorganic salts, polyethylene glycol stearate, viscosity modifiers such as ethanol, pearling agents, fragrances, pigments, antioxidants ; Montmorillonite, saponite, hex , Water-swelling clay minerals such as veegum, kunivia and smecton; polysaccharides such as carrageenan, xanthan gum, sodium alginate, pullulan, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxyvinyl polymers, polyvinylpyrrolidone and other synthetic polymers Other polymers such as; titanium oxide, kaolin, mica, sericite, zinc white, talc and other extender pigments, polymethylmethacrylic acid, nylon powder and other polymer powder pigments, etc. It can be appropriately blended within a range that does not impair it.

The cosmetic of the present invention can be produced by a usual method, and its dosage form can be any dosage form such as liquid, cream, solid, powder, etc. It is preferably creamy.

When the compound (1) of the present invention is used as an intermediate for producing an etherified polyhydric alcohol, the compound (1) of the present invention is preferably used in the presence of an acid catalyst or a basic catalyst, preferably a basic catalyst. In the presence, by hydrolysis,
Etherified polyhydric alcohols are easily obtained.

[0045]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In addition,
The gas chromatography in the following Reference Examples and Examples was carried out using GC-14A manufactured by Shimadzu Corp.
It was performed using icon SE 1% (φ2.6 mm × 0.5 m).

Reference Example 1 Synthesis of Pentaerythritol Monoacetate 408 g (3 mole) of pentaerythritol, 309 g (1 mole) of pentaerythritol tetraacetate and 0.4 g of sodium acetate were placed in a 2-liter four-necked flask at 170 ° C. under a nitrogen atmosphere. The mixture was reacted for 2 hours with stirring, and pentaerythritol monoacetate mixture 71
7 g were obtained. The results of analyzing the composition of this mixture by gas chromatography are shown in Table 1.

Reference Example 2 Synthesis of pentaerythritol monoacetate 544 g (4 mole) of pentaerythritol and 36 of acetic acid
Add 0g (6mole) to a 2 liter 4-neck flask,
Refluxed for 3 hours. Then, acetic acid was distilled off under reduced pressure,
664 g of pentaerythritol monoacetate mixture was obtained. The results of analyzing the composition of this mixture by gas chromatography are shown in Table 1.

[0048]

[Table 1]

From Table 1, it can be seen that the same composition can be obtained by any of the methods of Reference Example 1 and Reference Example 2.

Reference Example 3 Synthesis of pentaerythritol diacetate 136 g (1 mole) of pentaerythritol, 304 g (1 mole) of pentaerythritol tetraacetate and 0.4 g of sodium acetate were placed in a 1-liter four-necked flask and heated at 170 ° C. under a nitrogen atmosphere. The mixture was reacted for 2 hours with stirring, and pentaerythritol diacetate mixture 440
g was obtained. The results of analyzing the composition of this mixture by gas chromatography are shown in Table 2.

[0051]

[Table 2]

Reference Example 4 Synthesis of pentaerythritol monobutyrate 136 g of pentaerythritol, 132 g of butyric acid and 0.4 g of sodium acetate were placed in a 500 ml four-necked flask and refluxed for 2 hours. By distilling off the solvent, 224 g of a pentaerythritol monobutyrate mixture was obtained. The results of analyzing the composition of this mixture by gas chromatography are shown in Table 3.

[0053]

[Table 3]

Example 1 71.3 g of the pentaerythritol monoacetate mixture obtained in Reference Example 1 and 0.04 g of sodium acetate were added to 30 parts.
It was put in a 0 ml four-necked flask and heated to 170 ° C. to dissolve it. Then, dry nitrogen gas was blown in, 65.2 g of isostearyl glycidyl ether was added dropwise over 30 minutes, and then the mixture was reacted at 170 ° C. for 6 hours with stirring. Next, the obtained product is separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 1), and pentaerythritol monoisostearyl glyceryl ether monoacetate (purity 99% or more by liquid chromatography analysis). ) 34 g (33% yield) were obtained. Saponification number 112 (calculated value 111) ¹ H-NMR (CDCl ₃ ): δ (ppm) 3.3 to 4.0 (m, -OCH ₂ -,-CHOH-), 2.1 (s, -OCOCH ₃ ), 1.3 to 1.6
(b, -CH ₂ -,-CH-), 0.9 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200 to 3400 ν (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2850, 2920 ν (C = O) 1750, 1250 ν (Bend) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460 ν (-CO-) 1110, 1035, 1010

Example 2 44 g of the pentaerythritol diacetate mixture obtained in Reference Example 3 and 0.21 g of thorium acetate were mixed with 200 ml of 4 parts.
It was put in a one-necked flask and heated to 130 ° C. to dissolve it.
After that, dry nitrogen gas was blown in, and 33 g of isostearyl glycidyl ether was added dropwise over 30 minutes, and then 130
The reaction was carried out at 6 ° C with stirring for 6 hours. Next, the obtained product is separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 1), and pentaerythritol monoisostearyl glyceryl ether diacetate (purity 99% or more by liquid chromatography analysis). ) 20 g (37% yield) were obtained. Saponification number 205 (calculated value 206) ¹ H-NMR (CDCl ₃ ): δ (ppm) 3.3 to 4.1 (m, -OCH ₂ -,-CHOH-), 2.1 (s, -OCOCH ₃ ), 2.2 (s, -
OCOCH ₃ ), 1.3 to 1.6 (b, -CH ₂ -,-CH-), 0.9 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200 to 3400 ν (stretching) ( -CH-,-CH ₂ -,-CH ₃ ) 2850, 2920 ν (C = O) 1740, 1250 ν (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460 ν (- CO-) 1110, 1035, 1010

Example 3 35.7 g of the pentaerythritol monoacetate mixture obtained in Reference Example 2 and 0.02 g of sodium acetate were added to 20 parts.
It was put in a 0 ml four-necked flask and heated to 170 ° C. to dissolve it. Then, dry nitrogen gas was blown in, and 18.6 g of octyl glycidyl ether was added dropwise over 30 minutes,
The reaction was carried out at 170 ° C. for 6 hours with stirring. Then, the obtained product is separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 1), and pentaerythritol monooctyl glyceryl ether monoacetate (purity 99% or more by liquid chromatography analysis) 12 g (yield 34%) was obtained. Saponification number 155 (calculated value 154) ¹ H-NMR (CDCl ₃ ): δ (ppm) 3.3 to 4.0 (m, -OCH ₂ -,-CHOH-), 2.1 (s, -OCOCH ₃ ), 1.3 to 1.
6 (b, -CH ₂ -,-CH-), 0.9 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200 to 3400 ν (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2850, 2920 ν (C = O) 1750, 1250 ν (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460 ν (-CO-) 1110, 1035 , 1010

Example 4 200 g of 41 g of the pentaerythritol monobutyrate mixture obtained in Reference Example 4 and 0.02 g of sodium acetate were added.
In a four-necked flask, and heated to 130 ° C. to dissolve. Then, dry nitrogen gas was blown in, and 33 g of stearyl glycidyl ether was added dropwise over 30 minutes, and then 130
The reaction was carried out at 6 ° C with stirring for 6 hours. Then, the obtained product is separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 1), and pentaerythritol monostearyl glyceryl ether monobutyrate (purity 99% or more by liquid chromatography analysis). ) 18 g (yield 34%) was obtained. Saponification number 105 (calculated value 105) ¹ H-NMR (CDCl ₃ ): δ (ppm) 3.3 to 4.0 (m, -OCH ₂ -,-CHOH-), 2.2 (q, -OCOCH ₂ ), 1.3 to 1.
6 (b, -CH ₂ -,-CH-), 1.0 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200 to 3400 ν (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2850, 2920 ν (C = O) 1740, 1250 ν (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460 ν (-CO-) 1110, 1035 , 1010

Example 5 70.9 g of the pentaerythritol monoacetate mixture obtained in Reference Example 1 and 0.04 g of sodium acetate were added to 30 parts.
It was put in a 0 ml four-necked flask and heated to 170 ° C. to dissolve it. Then, dry nitrogen gas was blown in, and after 64.3 g of oleyl glycidyl ether was added dropwise over 30 minutes,
The reaction was carried out at 170 ° C. for 6 hours with stirring. Then, the obtained product is separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 1), and pentaerythritol monooleyl glyceryl ether monoacetate (purity 99% or more by liquid chromatography analysis) 30 g (yield 30%) was obtained. Saponification number 112 (calculated value 111) ¹ H-NMR (CDCl ₃ ): δ (ppm) 5.34 (m, -CH = CH-), 4.05 (s, -CH ₂ -OCO-), 3.3-4.0 (m, -OC
H ₂ -,-CHOH-), 2.03 (b, -CH ₂ -C =), 1.8 (s, -OCOCH ₃ ), 1.3 ~
1.6 (b, -CH ₂ -,-CH-), 0.9 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200 to 3400 ν (alkene CH stretch) 3048 ν (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2850, 2920 ν (C = O) 1750, 1250 ν (C = C expansion / contraction) 1644 ν (bend) (-CH-,-CH ₂ -,- CH ₃ ) 1375, 1460 ν (-CO-) 1110, 1035, 1010

Example 6 200 g of 48 g of the pentaerythritol monoacetate mixture obtained in Reference Example 1 and 0.1 g of sodium acetate were added.
In a four-necked flask, and heated to 170 ° C. to dissolve. Then, dry nitrogen gas was blown thereinto, and after adding 27 g of 2-hexadecyloxirane over 30 minutes, 170 ° C.
The mixture was reacted for 6 hours with stirring. Then, the obtained product was separated and purified by silica gel column chromatography (elution solvent: hexane: acetone = 1: 2), and mono-2-hydroxystearyl pentaerythryl ether monoacetate (purity by liquid chromatography analysis) 13% (yield 30%) was obtained. Saponification number 139 (calculated value 139) ¹ H-NMR (CDCl ₃ ): δ (ppm) 3.3 to 4.0 (m, -OCH ₂ -,-CHOH-), 2.1 (s, -OCOCH ₃ ), 1.3 to 1.
7 (b, -CH _2- ), 0.9 (m, -CH ₃ ) IR (liquid film) cm ^-1 : ν (-OH) 3200-3400 ν (stretching) (-CH-,-CH ₂ -,- CH ₃ ) 2860, 2920 ν (C = O) 1750, 1250 ν (Variation) (-CH-,-CH ₂ -,-CH ₃ ) 1380, 1460 ν (-CO-) 1110, 1040, 1005

Example 7 Using the compounds of the present invention obtained in Examples 1 to 6, hair rinse agents having the compositions shown in Table 4 were produced, and the rinse performance was examined. The results are shown in Table 4. (Manufacturing Method) To water heated to 70 ° C., components dissolved by being heated to the same temperature were added, stirred and mixed, and then cooled to room temperature with stirring to obtain a hair rinse agent. (Evaluation method) 20 g (15 cm in length) of hair of a Japanese woman who has never been subjected to cosmetic treatment such as cold perm or bleach has been bundled, and this hair bundle is commercial shampoo containing an anion activator as a main component. After the washing treatment, 2 g of the hair rinse agent shown in Table 4 was uniformly applied, followed by rinsing with running water for 30 seconds, and then towel drying. This wet hair bundle was subjected to a sensory evaluation for flexibility, smoothness and oiliness. The evaluation criteria were ⊚ for particularly excellent ones, ◯ for good ones, Δ for ordinary ones, and x for inferior ones.

[0061]

[Table 4]

Reference Example 5 713 g of the pentaerythritol monoacetate mixture obtained in Reference Example 1 and 0.41 g of sodium acetate were placed in a 3-liter four-necked flask and heated to 170 ° C. to dissolve them. Then, dry nitrogen gas was blown in, 652 g of isostearyl glycidyl ether was dropped over 30 times, and then the mixture was reacted at 170 ° C. for 6 hours with stirring. After the reaction was completed, 924 g of n-butanol and 1100 g of a 16% aqueous sodium hydroxide solution were added, and hydrolysis was carried out at 70 ° C. for 1 hour. After separating the layers, the organic layer is 1600 g of 0.5% bow glass water.
After that, the organic layer was washed and n-butanol was distilled off to obtain 840 g of isostearyl glyceryl etherified pentaerythritol. The results of analyzing the composition of this product by gas chromatography are shown in Table 5.

Reference Example 6 44 g of the pentaerythritol diacetate mixture obtained in Reference Example 3 and 0.21 g of sodium acetate were placed in a 200 ml four-necked flask and heated to 130 ° C. to dissolve them. Then, dry nitrogen gas was blown in, 33 g of isostearyl glycidyl ether was added dropwise over 30 minutes, and then 1
The reaction was carried out at 30 ° C. for 6 hours with stirring. After the reaction,
47 g of n-butanol and 110 g of a 16% aqueous sodium hydroxide solution were added, and hydrolysis was carried out at 70 ° C. for 1 hour. After separating the layers, the organic layer was washed with 160 g of 0.5% Bow's water and n-butanol was distilled off from the organic layer to obtain 42 g of isostearyl glyceryl etherified pentaerythritol.
The results of analyzing the composition of this product by gas chromatography are shown in Table 5.

Reference Example 7 44 g of the pentaerythritol diacetate mixture obtained in Reference Example 3 and 0.21 g of sodium acetate were placed in a 200 ml four-necked flask and heated to 170 ° C. to dissolve them. Then, dry nitrogen gas was blown in, 33 g of isostearyl glycidyl ether was added dropwise over 30 minutes, and then 1
The reaction was carried out at 70 ° C. for 6 hours with stirring. After the reaction,
47 g of n-butanol and 110 g of a 16% aqueous sodium hydroxide solution were added, and hydrolysis was carried out at 70 ° C. for 1 hour. After separating the layers, the organic layer was washed with 160 g of 0.5% Bow's water and n-butanol was distilled off from the organic layer to obtain 42 g of isostearyl glyceryl etherified pentaerythritol.
The results of analyzing the composition of this product by gas chromatography are shown in Table 5.

Comparative Reference Example 1 1090 g of pentaerythritol, 2720 g of dimethyl sulfoxide and 48% aqueous sodium hydroxide solution 16.
3 g was put into a 5 liter four-necked flask and heated to 90 ° C. to dissolve. Then, about 120 g of a mixture of water and dimethylsulfoxide was distilled off under reduced pressure to remove water in the reaction system. Next, dry nitrogen was blown in, the temperature was raised to 110 ° C., and then isostearyl glycidyl ether 652 was added.
g was added dropwise over 2 hours and then reacted at 110 ° C. for 3 hours with stirring. After the reaction was completed, 9.7 g of sulfuric acid was added to the reaction solution to neutralize the catalyst. Next, under reduced pressure, dimethylsulfoxide was completely distilled off at 80 ° C., 99% ethanol was added to the residue, and unreacted pentaerythritol was filtered off. Ethanol was distilled off from the obtained filtrate under reduced pressure, and 1000 ml of ethyl acetate and 1000 ml of water were added to the residue.
The extraction operation was performed by adding ml. After partitioning, ethyl acetate was distilled off from the organic layer to obtain 842 g of isostearyl glyceryl etherified pentaerythritol. The results of analyzing the composition of this product by gas chromatography are shown in Table 5.
Shown in

Comparative Reference Example 2 The amount of pentaerythritol used was 545 g, and the reaction was 1
Isostearyl glyceryl etherified pentaerythritol 780 was prepared in the same manner as in Comparative Example 1 except that the treatment was carried out at 70 ° C.
g was obtained. The results of analyzing the composition of this product by gas chromatography are shown in Table 5.

[0067]

[Table 5]

Reference Example 8 53.6 g of a glycerin monoacetate mixture obtained in the same manner as in Reference Example 2 except that 4 mol of glycerin was used instead of pentaerythritol and 0.4 g of sodium hydroxide.
Was placed in a 200 ml four-necked flask and heated to 130 ° C. to dissolve it. Then, dry nitrogen gas was blown in, 37.2 g of octyl glycidyl ether was added dropwise over 2 hours, and then the mixture was reacted at 130 ° C. for 4 hours with stirring. After completion of the reaction, 100 g of hexane and 110 g of 16% sodium hydroxide aqueous solution were added, and hydrolysis was carried out at 70 ° C. for 1 hour.
After the layer separation, the organic layer was washed with 160 g of 0.5% bow glass water,
Hexane was distilled off from the organic layer to obtain 60.9 g of octyl glyceryl etherified glycerin. The results of gas chromatography analysis of the composition of this product are shown in Table 6.

Comparative Reference Example 3 Glycerin 920 g, sodium hydroxide aqueous solution 8.0 g
Was placed in a 2-liter four-necked flask and heated to 110 ° C. to dissolve it. Then, about 20 g of a mixture of water and glycerin was distilled off under reduced pressure to remove water in the reaction system. Next, dry nitrogen was blown in, the temperature was raised to 110 ° C., and then
After 37.2 g of octyl glycidyl ether was added dropwise over 2 hours, the mixture was reacted at 110 ° C. for 5 hours while stirring.
After the reaction was completed, 9.9 g of sulfuric acid was added to the reaction solution to neutralize the catalyst. Next, glycerin was completely distilled off under reduced pressure, and 300 ml of ethyl acetate and 1000 ml of water were added to the residue for extraction. After the layers were separated, ethyl acetate was distilled off from the organic layer to give octyl glyceryl etherified glycerin 60.2.
g was obtained. The results of gas chromatography analysis of the composition of this product are shown in Table 6.

[0070]

[Table 6]

Reference Example 9 94.4 g of a mixture of methyl glucoside monoacetate obtained in the same manner as in Reference Example 2, except that 4 mol of methyl glucoside was used instead of pentaerythritol, 200 g of dimethyl sulfoxide and 2.8 g of potassium hydroxide were added to 500 parts.
The mixture was placed in a ml flask and heated to 120 ° C. to dissolve it, and dry nitrogen gas was blown into it to distill about 20 g of water and dimethyl sulfoxide to remove water in the reaction system. 33 g of 2-heptylundecyl glycidyl ether was dropped into the flask over 2 hours, and then reacted at 120 ° C. for 6 hours while stirring. After completion of the reaction, 200 g of isobutanol and 110 g of a 16% sodium hydroxide aqueous solution were added, and hydrolysis was carried out at 30 ° C. for 1 hour. After the layers were separated, the organic layer was washed with 160 g of 0.5% bow glass water, and isobutanol was distilled off from the organic layer to obtain 56 g of 2-heptylundecylglyceryl etherified methyl glucoside. Table 7 shows the results of analysis of the composition of the product by gas chromatography.

Comparative Reference Example 4 Methyl glucoside 194 g, dimethyl sulfoxide 40
0 g and 2.8 g of potassium hydroxide were placed in a 1 liter flask, heated to 120 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 50 g of water and dimethyl sulfoxide to remove water in the reaction system. . 33 g of 2-heptylundecyl glycidyl ether was dropped into the flask over 2 hours, and then reacted at 120 ° C. for 6 hours while stirring. After completion of the reaction, 3 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and ethanol was added to the residue.
00 ml was added and the precipitated methyl glucoside was filtered off.
Ethanol was distilled off from the filtrate to obtain 56 g of 2-heptylundecylglyceryl etherified methyl glucoside.
Table 7 shows the results of analysis of the composition of the product by gas chromatography.

[0073]

[Table 7]

Reference Example 10 95 g of a tetraglycerin monoacetate mixture obtained in the same manner as in Reference Example 2 except that 4 mol of tetraglycerin was used instead of pentaerythritol and 1.0 g of potassium hydroxide were placed in a 300 ml flask and heated to 100 ° C. It was heated and dissolved. Then, dry nitrogen gas was blown into the flask, and 33 g of isostearyl glycidyl ether was placed in the flask.
After dropping over a period of time, the mixture was reacted at 110 ° C. for 4 hours with stirring. After the reaction was completed, 100 g of n-butanol and 110 g of a 16% aqueous sodium hydroxide solution were added, and hydrolysis was carried out at 70 ° C. for 1 hour. After the layers were separated, the organic layer was washed with 160 g of 0.5% Bow's water and n-butanol was distilled off from the organic layer to obtain 61 g of isostearyl glyceryl etherified tetraglycerin. The results of gas chromatography analysis of the composition of this product are shown in Table 8.

Comparative Reference Example 5 Tetraglycerin 157 g, N-methylpyrrolidone 10
0 g and 1.0 g of potassium hydroxide were put into a 300 ml flask, heated to 100 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 10 g of water and N-methylpyrrolidone to remove water in the reaction system. did. After 33 g of isostearyl glycidyl ether was added dropwise to the flask over 5 hours, the mixture was reacted at 110 ° C. for 4 hours with stirring. After the reaction was completed, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then N-methylpyrrolidone was added under reduced pressure to 8
It was completely distilled off at 0 ° C., and 500 ml of methyl ethyl ketone and 1000 ml of water were added to the residue for extraction. Methyl ethyl ketone was distilled off from the obtained methyl ethyl ketone soluble part under reduced pressure to obtain 61 g of isostearyl glyceryl etherified tetraglycerin. The results of gas chromatography analysis of the composition of this product are shown in Table 8.

[0076]

[Table 8]

Reference Example 11 713 g of the pentaerythritol monoacetate mixture obtained in Reference Example 2 and 0.41 g of sodium acetate were placed in a 3-liter four-necked flask and heated at 170 ° C. to dissolve them. Then, dry nitrogen gas was blown in, and 256 g of 2-hexyloxirane was added over 30 minutes.
The reaction was carried out at 0 ° C. for 6 hours with stirring. After completion of the reaction, n
-Butanol 600g and 16% sodium hydroxide aqueous solution 1100g were added, and it hydrolyzed at 80 degreeC for 1 hour. After the layer separation, the organic layer was washed with 1600 g of 0.5% bow glass water,
Butanol was distilled off from the organic layer to obtain 475 g of 2-hydroxyoctyl etherified pentaerythritol. The results of gas chromatography analysis of the composition of this product are shown in Table 9.

Comparative Reference Example 6 545 g of pentaerythritol, 2720 g of dimethyl sulfoxide and 48% aqueous sodium hydroxide solution 16.3
g was placed in a 5 liter four-necked flask and heated to 90 ° C. to dissolve. Then, about 120 g of a mixture of water and dimethylsulfoxide was distilled off under reduced pressure to remove water in the reaction system. Next, dry nitrogen was blown in, the temperature was raised to 170 ° C., 256 g of 2-hexyloxirane was added over 2 hours, and then the mixture was reacted at 170 ° C. for 3 hours while stirring. After the reaction was completed, 9.7 g of sulfuric acid was added to the reaction solution to neutralize the catalyst. Next, under reduced pressure, dimethylsulfoxide was completely distilled off at 80 ° C., 99% ethanol was added to the residue, and unreacted pentaerythritol was filtered off. After ethanol was distilled off from the obtained filtrate under reduced pressure, 1000 ml of ethyl acetate and 1000 ml of water were added to the residue for extraction. After the layers were separated, ethyl acetate was distilled off from the organic layer to obtain 410 g of 2-hydroxyoctyl etherified pentaerythritol. The results of gas chromatography analysis of the composition of this product are shown in Table 9.

[0079]

[Table 9]

Reference Example 12 704 g of the pentaerythritol monoacetate mixture obtained in Reference Example 1 and 0.4 g of sodium acetate were placed in a 3-liter four-necked flask and heated to 170 ° C. to dissolve them. After that, dry nitrogen gas was blown in, 647 g of oleyl glycidyl ether was added dropwise over 30 minutes, and then 17
The reaction was carried out at 0 ° C. for 6 hours with stirring. After completion of the reaction, n
-Butanol (920 g) and 16% sodium hydroxide aqueous solution (1100 g) were added, and hydrolysis was carried out at 70 ° C for 1 hour. After the layer separation, the organic layer was washed with 1600 g of 0.5% bow glass water,
N-Butanol was distilled off from the organic layer to obtain 810 g of oleyl glyceryl etherified pentaerythritol. Table 10 shows the results of the gas chromatography analysis of the composition of this product.

Comparative Reference Example 7 1090 g of pentaerythritol, 2720 g of dimethyl sulfoxide, and 48% aqueous sodium hydroxide solution 16.
3 g was put into a 5 liter four-necked flask and heated to 90 ° C. to dissolve. Then, about 120 g of a mixture of water and dimethyl sulfoxide was distilled off under reduced pressure to remove water in the reaction system. Next, dry nitrogen was blown in and the temperature was raised to 110 ° C., and then 648 g of oleyl glycidyl ether was added.
After dropping over a period of time, the mixture was reacted with stirring at 110 ° C. for 3 hours. After the reaction was completed, 9.5 g of sulfuric acid was added to the reaction solution to neutralize the catalyst. Next, under reduced pressure, at 80 ° C., 9.5 g of sulfuric acid was added to dimethyl sulfoxide to neutralize the catalyst. Next, under reduced pressure, dimethylsulfoxide was completely distilled off at 80 ° C., 99% ethanol was added to the residue, and unreacted pentaerythritol was filtered off. After ethanol was distilled off from the obtained filtrate under reduced pressure, 1000 ml of ethyl acetate and 1000 ml of water were added to the residue for extraction. After the layers were separated, ethyl acetate was distilled off from the organic layer to obtain 833 g of oleyl glyceryl etherified pentaerythritol.
I got Table 10 shows the results of the gas chromatography analysis of the composition of this product.

[0082]

[Table 10]

[0083]

INDUSTRIAL APPLICABILITY The etherified polyhydric alcohol fatty acid ester (1) of the present invention is useful as an intermediate for producing an etherified polyhydric alcohol used as a cosmetic ingredient, and the efficiency can be improved by passing through the compound (1). It is possible to produce an ether alcohol having a desired degree of etherification well, and it itself has excellent properties as a base material for cosmetics, an emulsifier, a lubricant, an oil agent, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 69/22 69/30 69/33 C07H 13/06

Claims (8)

[Claims] 1. An etherified polyhydric alcohol fatty acid ester represented by the following general formula (1). G (A) _x (B) _y (1) [In the formula, G represents a residue excluding hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having three or more hydroxyl groups, and x A's are the same. However, the following general formula may be used. (R represents R ′ or —CH ₂ OR ′ (R ′ represents a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms).)
And y's, which may be the same or different, each represents a hydrogen atom or an acyl group having 1 to 11 carbon atoms, at least one of which is an acyl group. x and y each represent a number of 1 or more, the sum of which is the number of hydroxyl groups of the polyhydric alcohol in G. ] 2. The etherified polyhydric alcohol fatty acid ester according to claim 1, wherein B in the general formula (1) is a hydrogen atom or an acyl group having 2 to 4 carbon atoms. 3. G in the general formula (1) is pentaerythritol, sorbitol, mannitol, glycosides,
Glycerin and the following general formula: (In the formula, a represents a number of 2 to 20), which is a residue obtained by removing hydrogen atoms from all hydroxyl groups of a polyglycerin selected from polyglycerin and alkylene oxide adducts thereof. Item 1. An etherified polyhydric alcohol fatty acid ester according to item 1 or 2. 4. G in the general formula (1) is pentaerythritol, glycerin and the following general formula: (In the formula, b represents a number of 2 to 4.) A residue obtained by removing a hydrogen atom from all hydroxyl groups of a polyhydric alcohol selected from polyglycerin represented by the formula 1.
The etherified polyhydric alcohol fatty acid ester described. 5. In the general formula (1), R'is represented by the following general formula (a) or (b): (In the formula, p and q each represent an integer of 0 to 33 whose sum is 13 to 33, and r and s have a sum of 11 to 11).
31 is an integer of 0 to 31, respectively. And an etherified polyhydric alcohol fatty acid ester according to any one of claims 1 to 4, which is an alkyl group represented by the formula (4). 6. The etherified polyhydric alcohol fatty acid ester according to claim 1, wherein R'in the general formula (1) is an oleyl group. 7. A compound represented by the following general formula (2) G (B) _z (2) (wherein G is a residue of a polyhydric alcohol having three or more hydroxyl groups excluding hydrogen atoms of all hydroxyl groups). Where B is a hydrogen atom or an acyl group having 1 to 11 carbon atoms, z is the number of hydroxyl groups of the polyhydric alcohol in G. z is B, at least one hydrogen atom and one acyl group. And a polyhydric alcohol fatty acid ester represented by the following general formula (3) [Wherein R is R'or -CH ₂ OR '(R' is a carbon number of 1 to 36)
The linear or branched alkyl group or alkenyl group) is shown. ] The following general formula (1) G (A) _x (B) _y (1) characterized by reacting an epoxy compound represented by the formula: [wherein G and B have the same meanings as described above, x The A's may be the same or different and may be represented by the following general formula: (R represents the same meaning as described above.),
y B's may be the same or different and at least one is an acyl group. x and y are each 1 whose sum is z
The above numbers are shown. ] The manufacturing method of etherified polyhydric alcohol fatty acid ester represented by these. 8. A cosmetic containing the etherified polyhydric alcohol fatty acid ester according to claim 1.